Aliphatic and alicyclic amines

Toxicity Acute, prolonged exposure in workplaces has caused a variety of health disorders in workers (e.g., erythema, edema, skin peeling, loss of appetite, muscle weakness, paresthesia, CNS depression, peripheral nerve disorders, skin and respiratory irritation, chemical pneumonia in children).7 In addition, rubber solvents, varnish, thinners, and petroleum spirits cause skin irritation, respiratory problems, and hematologic effects in workers all demand proper handling and chemical safety. 

Uses Kerosene is a white to pale yellow, flammable liquid in wide use in household and industrial activities (e.g., heating, cooking fuel, cleaning, degreasing, as a solvent for paints, enamels, polishes, and varnishes, and in asphalt coating). 

Aliphatic and alicyclic amines form one of the most extensively used categories of compounds in a variety of manufacturing industries. These compounds are first-phase materials for chemical synthesis, intermediates, pharmaceuticals, pesticides, soil sterilizers, and several kinds of solvents, rubber products, rocket propellants, and plastic monomers. This chapter discusses the safety and toxicity of selected compounds handled by workers in different industries. More information and extensive literature are available in several study reports on members of this important group.31,32 

Methylamine (Aminomethane, Methanamine, Monomethylamine) Molecular formula CH3NH2 

Uses Methylamine is a colorless, fishlike-smelling gas at room temperature. It is used in a variety of industries such as manufacture of dyestuffs, treatment of cellulose, acetate rayon, fuel additive, rocket propellant, and leathertanning processes. 

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We now turn to the subject of aromatic amines. The number of classes of aromatic species vastly exceeds the number of classes of aliphatic and alicyclic amines. We somewhat arbitrarily consider mixed aromatic/ ali- species such as 7V,7V-dimethylaniline and 7V-methyldiphenylamine as aromatic and so they accompany the totally aromatic triph-enylamine instead of joining the totally ali- species trimethylamine. However more numerous the compounds of potential interest, the number of relevant aromatic species for which there are appropriate thermochemical data is also few. 

Good yields of secondary amines are achieved using both the methods in the reactions of aromatic and aliphatic aldehydes as well as of diaUcyl ketones and cycloalkanones with aliphatic and alicyclic amines (and ammonia). Anilines give low yields, but when 2 equiv is used in the sodium hydrogen telluride method, the yields are improved. In the reaction of ammonia with aldehydes, symmetrical secondary amines are obtained, whereas glu-taraldehyde and amines lead to N-substituted piperidines. 

Beard RR, Noe JT Aliphatic and alicyclic amines. In Clayton GD, Clayton FE (eds) Patty s Industrial Hygiene and Toxicology, 3rd ed, rev, Vol 2B, Toxicology, pp 3135-3155. New York, Wiley-Intersdence, 1981... 

Sutton WL Aliphatic and alicyclic amines. In Fassett DW, Irish DD (eds) Industrial Hygiene and Toxicology, 2nd ed, Vol. 2, Toxicology, p 2045. New York, Interscience, 1963... 

NitroaUcanes. Primary aliphatic and alicyclic amines are oxidized by /-BuOOH in the presence of (t-BuO),jZr and 3A molecular sieves in dichloromethane. 

Cleavage of tertiary amines.1 Tertiary aliphatic and alicyclic amines can be dealkylated by reaction with phenyl chloroformate in methylene chloride at 10-40°... 

Of the aliphatic and alicyclic amines, the optimal length of the chain should have seven or eight carbon atoms. Any decrease or increase in the number of carbon atoms results in lowering of the intensity of pressor action. Thus isoamylamine or 4-methyl-2-aminooctane is decidedly less active than forthane or clopane. Prolonged duration of action is acquired by the presence of a methyl group adjacent to the nitrogen atom. Such compounds tend to produce tachyphylaxis and inhibit amine oxidase. 

Of the number of chromophoric derivatives of chiral amines for potential use in the establishment of their absolute configuration by BCD measurement only a few have proven to be generally useful. Of these, intensive investigation of the Af-salicylidene (Schiff base) derivatives of chiral primary amines, including unsubstituted and ring-substituted a- and S-arylalkylamines, a-amino acids, unsaturated and satnrated aliphatic and alicyclic amines, and amino sugars, has resulted in the formulation of the salicylidenamino chirality rule ° °. The application of this rule has recently been reviewed and has been successfully used for the establishment of absolute configuration of chiral primary amines in connection with other stereochemical studies. In related studies, the conformations of a series of pyridoxyl-L-a-amino acid Schiff bases were deduced from their CD spectra ... 

Phenyl ester [1885-14-9]. Phenyl chloroformate. Used for cleavage of tertiary aliphatic and alicyclic amines. Bp9 68-71 . 

Nitroprnsside(sodiiim)-aeetaldehyde for secondary aliphatic and alicyclic amines. 

More widely used as a source of aliphatic and alicyclic amines is the reduction of azides (reaction 93), many of which are available by... 

The reaction of phenyl chloroformate with tertiary aliphatic and alicyclic amines to give the corresponding N-carboxylates (pathway a) is an efficient general procedure for cleavage of tertiary amines, and provides a convenient alternative to the weil-known von Braun cyanogen bromide cleavage. The choice of phenyl chloroformate over alkyl esters in this reaction probably results in suppression of the undesired competitive reaction pathway b. 

Reductive C-N bond cleavage has been demonstrated in more complex systems using ethyl chloroformate as a solvent. Chlorination of corticosteroid cyclic ethers has been observed. Tertiary aliphatic and alicyclic amines can be dealkylated. Phenyl chloroformate, however, is usually regarded as the reagent of choice. In summary, deamination, demethylation, debenzylation, and deal-lylation of tertiary amines can all occur on treatment with ethyl chloroformate but the regioselectivities of these reactions are difficult to predict. ... 

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